ESL-IE-84-04-88

GAS-ADSORPTION PROCESSES - AN UPDATE

George E. Keller II

Union Carbide Corporation

South Charleston. West Virginia

ABSTRACT
Gas-adsorption processes are commonly used
in the petroleum. natural-gas, petrochemical and
other industries. It is important to be aware
of those process situations which favor the use
of adsorption, and although no hard and fast
rules can be given. some generalizations can be.
and the first part of the paper is devoted to a
discussion of these generalizations. Adsorption
processes come in a wide range of physical
embodiments. These embodiments are first
discussed as idealizations, and their strong
points and weak points are delineated. Next,
several specific process flowsheets which have
been commercialized rather recently and which
may be extrapolable to other separations are
discussed. Finally, the issue of where
gas-adsorption technology is headed is
confronted. Suggestions are made as to possible
new and expanded applications.

which have been commercialized will be

discussed. and. finally. some suggestions will
be made as to directions in which the technology
is moving and opportunities for expanded
applications for gas adsorption.
WHEN CAN ADSORPTION COMPETE?
Gas adsorption's chief competitors are
obviously the vapor-liquid separations and. more
recently, membrane-based processes.
Vapor-liquid processes are formidable
competitors because of their simple flowsheets;
this translates into relatively low capital
costs per unit of feed processed. Given the
importance of capital costs in overall process
economics, vapor-liquid separations will usually
be a first choice if the energy costs are
tolerable. And in fact, systems of distillation
columns can often be heat-integrated to reduce
energy costs, further increasing their economic
viability in competition with other separations.

INTRODUCTION
Distillation and related vapor-liquid-based
separations (absorption and azeotropic and
extractive distillation) are by far the most
widely used separation processes in the
natural-gas, petroleum, petrochemical and
related industries. In addition, vapor-liquid
based separations have been practiced for
several hundred years. and they are probably
approaching a technological asymptote. By
contrast, adsorption has been practiced, except
for a few instances such as solution
clarification and for air purification in
hospitals and on battlefields, for only about 60
years. But in this relatively short time, and
having approached much less closely its
technological asymptote, adsorption now ranks
second to vapor-liquid-based separations in
frequency of use in the above-named industries.

Nevertheless, there clearly are situations

for which adsorption is the proper choice.
Although we cannot cite precise criteria, we can
enumerate several rough criteria. In the
following list, distillation is assumed to be
the chief competitor, and it is also assumed
that an adsorbent with proper selectivity
(greater than two for the adsorbate over
less-adsorbing components) is available.
1. The relative volatility for distillation is
low - 1.2-1.5 or less.
2. Several components must be separated from
other components boiling in among the components
to be separated.
3. Pressures greater than about 40 to 60
atmospheres (and especially if the feed gas is
substantially lower in pressure than the column
pressure) and/or cryogenic temperatures must be
used.

In this paper we will first describe those

process conditions which favor the use of gas
adsorption. We will then describe several
archetype processes and delineate their strong
and weak points. Next some specific variations

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Proceedings from the Sixth Annual Industrial Energy Technology Conference Volume II, Houston, TX, April 15-18, 1984

ESL-IE-84-04-88

Pressure-Swing Adsorption (PSA~ - In this cyle,

shown in its simplest form in igure 2, the!
adsorbate is desorbed by lowering its partial
pressure, partly by reducing total pressure and
partly by using some of the non-adsorbate as a
partial-pressure-reducing purge gas. Usually
PSA processes employ at least three beds in '
parallel, with several purging and
.
blowdown/repressurization steps to minimize feed
compression costs and maximize less-adsorbed
product recovery.

4. Thermal damage to the products or rapid

column fouling occurs at practical distillation
conditions.
Criteria for selecting between adsorption
and membrane-based processes are not yet
available, and the proper choice must be made on
a case-by-case analysis.
ARCHETYPE PROCESSES
Four archetype processes will be briefly
discussed here. These processes differ
primarily in the means by which desorption is
effected. In a following section we will show
some recent process modifications.

Less-Adsorbed
Product

Temperature-Swing Adsorption - A schematic

diagram is shown in Figure 1. Once a bed is
loaded with adsorbate, it is taken off-line and
regenerated by heating and (almost always)
purging with an inert gas. Increasing the
adsorbent temperature reduces the tenacity of
the adsorbate-adsorbent bonds, and the inert gas
reduces the partial pressure of adsorbate; both
effects serve to facilitate desorption.

rn
D

The advantages of this process are that high

degrees of separation are possible and that
investments are usually reasonable. The
disadvantages are that the energy usage is very
high per unit of adsorbate and that regeneration
times are long - several hours to a day or
more. As a result, this cycle is economical
only for removing small amounts (generally a few
weight percent or less) of materials from feed
streams.
Less-Adsorbed
Product

rn
D

Adsorba1e
Plus Le~s
Adsorbed
Product
Purge Gas

Pressurized
Feed

Purge Gas
Figure 2.

PSA Cycle

Heater
The advantages of PSA are that it can
perform bulk separations (those for which t~e
adsorbate concentration is greater than about 10
weight percent) and that investments are
competitive with alternative processes. The
chief disadvantage is that only the
less-adsorbed product can be recovered in h~gh
purity; the adsorbed product inevitably con~ains
some of the less-adsorbed product used as a I
purge. Desorption under vacuum can reduce
adsorbed-product contamination, however.

Inert-Purge Adsorption - This cycle, shown in

Figure 3, operates adiabatically and uses an
inert gas to lower the partial pressure of ~he
adsorbate and desorption. Occasionally total
pressure will be reduced.

Vent

Cooler
Possible
Recycle

The chief advantages are process simplicity,

leading to low investment, and the ability to
perform bulk separations in some cases. Th~
disadvantages are the large exotherms, which
limit the adsorbate loading, the fact that very
large amounts of inert gas must be used if the
adsorbate is tightly held, and the problem of
recovery of the adsorbate from the inert gas.

Adsorbate

Feed
Figure 1.

Temperature-Swing Cycle

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Proceedings from the Sixth Annual Industrial Energy Technology Conference Volume II, Houston, TX, April 15-18, 1984

ESL-IE-84-04-88

Less-Adsorbed
rroduct

The chief advantages are elimination of the

exotherm, which makes higher loadings possible,
and the ability to perform bulk separations.
The disadvantages are process complexity, which
leads to high investment, and the energy
requirement to operate the stills.

Purge
Gas

Conclusion - Compared to distillation,

gas-adsorption technology is substantially more
varied, and clearly one flowsheet cannot be used
for all separations. One must therefore be
prepared to deal with both adsorbent development
and flowsheet selection and development to
effect a successful process development.

NEW DEVELOPMENTS

In this section we will highlight some

recent developments - variations on the
archetype processes - which either increase the
number of separations amenable to adsorption or
improve the economics of the archetype processes.

Adsorbate
Plus
Purge Gas

Feed

Figure 3.

Continuous Temperature-Swing Adsorption - All of

the archetype processes are discontinuous:
adsorbate is first loaded and then desorbed in a
fixed bed. The idea of performing continuous
adsorptions by moving the adsorbent between
adsorption and desorption zones is far from new
and extends at least back to the 1930s. In 1950
the Hypersorption process was developed by Union
Oil Company [1,2]. This process foundered
because of excessive attrition of the
activated-carbon adsorbent. Recently Kureha
Chemical Company, Ltd., of Japan has developed a
hard, microspherical activated carbon called
bead activated carbon (SAC). This development
has made possible a fluidized-bed/moving-bed
process, shown in Figure 5, for removin9 small
amounts (less than a few weight percent) of
adsorbates from feed streams. The process,
called GASTAK in Japan [3] is marketed in the
United States under the name PURASIV HR [4,5] by
Union Carbide. There are presently 12 operating
units in the United States and over 40 in
Japan. The units in the United States treat
from 300 thousand to 5.5 million cubic feet per
hour of feed, removing such materials as
hydrocarbons and oxygenated and chlorinated
hydrocarbons.

Inert-Purge Cycle

~lacement-Purge Adsorption - This final

archetype cycle, shown in Figure 4, is similar
in concept to inert~purge adsorption except that
the displacement medium competitively adsorbs
with adsorbate and effects desorption both by
partial-pressure reduction and by mass action.
The displacement medium boils outside the range
of the products and is recovered from the
products by distillation.
A = Adsorbates

B = Less-adsorbed components

C = Displacement agent

D
B+D

Nitrogen Recovery - Bergbau Forschung GmbH has

developed a process for recovering nitrogen from
air in up to 99.9 percent purity using a
PSA-type cycle with vacuum desorption [6,7].
The adsorbent is a unique carbon molecular sieve
which separates on the basis of differing
diffusion rates in the adsorbent pores rather
than on inherent equilibrium selectivity; the
carbon is virtually non-selective at
equilibrium. Under diffusion control, however,
oxygen penetrates into the particles much faster
than nitrogen, leaving a nitrogen-enriched,
gas-phase product. Nitrogen production using
carbon molecular sieves is the only known
commercial process using diffusion-selectivity
as the basis for separation.

~
~

~
~

~
~

Feed
A+B

A+D

D
Figure 4.

Displacement-Purge Cycle

521

Proceedings from the Sixth Annual Industrial Energy Technology Conference Volume II, Houston, TX, April 15-18, 1984

ESL-IE-84-04-88

"POLYBEO" PSA - Usually in the design of a

process, the simpler the flowsheet, the better
the economics. An exception to this generality
is the POLYBED PSA process for hydrogen recovery,
commercialized by Union Carbide [10-12J.
Normally P5A processes will consist of four or
fewer beds in parallel; POLYBEO PSA USes five
and in some cases even over 10 beds in parallel.
In addition, the process involves extensive gas
interchanges and pressure eQuiliz tions between
the beds. The net result is a process which can
treat very large feed streams (up to about two
million standard cubic feet per hour in a single
train), recover higher percentages of hydrogen
in the feed (about 86 percent vs. 70 to 75
percent for more conventional PSAs), and produce
astoniShingly pure hydrogen (e.g., 99.999
percent) .

Less-Adsorbed Gas

Feed

.~

Steam

~.

Azeotrope Breaking - Some of the more cos ly

mixtures for separation by vapor-liquid means
are azeotrope-forming solutions. Extractive or
azeotropic distillation must be used, and
several columns must be used. Quite recently a
new adsorption-based process has surfaced which
is especially suited for separating aQueous
organic mixtures containing up to 20 or more
weight percent water [13J. An inert-purge cycle
is used, and in the example discussed, carbo~
dioxide or nitrogen is used as the purge gas for
separating the ethanol-water azeotrope using
molecular sieves. The important feature of the
process is that most of the heat of adsorption
is stored in the bed during the adsorption p~rt
of the cycle, and that heat is then available
for the subsequent desorption of the water. The
net result is tha , along with an investment
lower than that of azeotropic distillation, ohe
energy requirement is less than 2000 Btu/gal.
The process is being commercialized.

Recovered
Solvents

1 - - - ...

Condensa te
Li ft

Gas

Figure 5.

PURASTV HR Process

H20/C0 2
Separation Section
,.-______
Removal
,------.---...,. - - -

Other methods of using PSA for obtaining

nitrogen from air have been revealed by Toray
Industries, Inc. [8J and Air Products Corp. [9J.
These processes, by adjusting feed and purge
flows, produce a relatively pure adsorbate
(nitrogen) stream and a relatively impure less
adsorbed (oxygen) stream, using more traditional
moleculat" sieve adsorbents. A diagram of the
Toray process is shown in Figure 6. Dried air
is passed through the absorber at super
atmospheric pr ssure, and nitrogen is
preferentially adsorbed. Part of the nitrogen
product from previous cycles is then passed into
the bed to desorb small amounts of oxygen, after
which the bed is reduced to atmospheric pressure
to desorb nitrogen. Finally more nitrogen is
recovered by vacuum desorption. The adsorbent
used in this process is apparently the same
zeolite molecular sieves - as that used in
oxygen PSA processes.

--'A.~

,-

.,

I
I
I

rn

c
Ol
Ol

C
Ol

>-

::;)

0..

.D

.n

>-

Vl

>

Vl
C1)

OJ
0

1--
I
I - - - -_ _ .....
I
L..... -

..A

------~R-e~fl:-u-x---..6

Pressurized Ai r

This process has been demonstrated in

pilot-scale. Its commercial status is unknown.
The Air Products process has been commercialized.

Figure 6.

Toray Nitrogen Process

522
Proceedings from the Sixth Annual Industrial Energy Technology Conference Volume II, Houston, TX, April 15-18, 1984

ESL-IE-84-04-88

"TIP" Total Isomerization Process - Isomerization

reactions often have equilibrium limitations
which prevent attainment of one pure isomer.
This problem can be obviated if a separation
process can be coupled with the isomerization
step to remove selectively the isomer(s) of
interest. This has been done for paraffin
isomerization by combining the Hysomer paraffin
isomerization process. developed by Shell
Research BV, with Union Carbide's IsoSiv normal/
isoparaffin separation process [14J. The overall
process, known as the TIP Total Isomerization
Process, is shown in Figure 7. The Hysomer
reactor reacts the feed to a near-equilibrium
mixture of isomers, which is fed to the
adsorption unit. Normal paraffins are
preferentially adsorbed, and the isoparaffins
are recovered as a high-octane stream while the
adsorbed normal paraffins are desorbed by a
hydrogen purge and returned to the Hysomer unit.
Product from a TIP unit has a Research Octane
Number of 88 to 92, compared to a RON of 79 to
82 for the product from a Hysomer unit alone.

adsorption and suggest some technological

innovations which could stimulate this growth.
Bulk Gas Separations - Adsorption for oxygen and
nitrogen purification has been limited until
recently primarily to applications requiring a
few pounds to a few tons per day. Oxygen is now
produced via PSA for small steel mills,
waste-treatment plants, welding shops, and for
in-house care of patients with various types of
lung disease. On-board oxygen generation for
aircraft will soon be a reality. But as process
improvements continue, PSA oxygen will be able
to compete economically with cryogenically
produced oxygen in much larger plants - 100 tons
per day or more - in situations in which the
higher argon level in the PSA oxygen is not a
problem.
Nitrogen production via PSA is growing
rapidly, for such uses as inerting of storage
tanks and other vessels and areas, purging of
process lines and vessels, creating modified
atmospheres to prolong storage life in food
storage areas, etc. And if grain-storage
fumigants uch as ethylene dibromide come under
increasing environmental pressure, nitrogen
inerting may prove to be an ideal replacement
for use in enclosed areas.

Light
Pa ra Hi ns
H2 + Recycle
Normal Paraffins

Feed

PSA hydrogen recovery will also grow in

popularity in comparison to cryogenic methods.
It will be possible to process feed streams of
1.5 to three million standard cubic feet per
hour at pressures up to about 1000 psi. P A
will also be favored in cases in which the
virtual absence of inerts in the hydrogen
product would minimize purge stream losses in
other parts of the process.

C7\

.D

<..

Octane
Isomer
Produc t

Vl

-0

The major challenge for PSA is to produce

two nearly pure products at once in a simple
fashion; such a capability would allow PSA to
compete head-on with distillation for an
increasing number of separations. Increasing
the feed-to-purge pressure ratio is the primary
means for improving the purity of the adsorbed
product. Desorption under vacuum is one means
though not without added costs - for increasing
this ratio. Other PSA cycles not involving the
need for high ratios would constitute a true
breakthrough.

Heater

Figure 7.

TIP Total Isomerizc.tion Process

Inert-purge cycles, given the

recently-demonstrated success in drying of
azeotropes, would seem to be poised for use in
several new separations. Prime candidates
include those systems now separated by
azeotropic and extractive distillation, many of
which contain water as one constituent. The use
of inert-purge cycles for isomer and other
close-boiler separations should also grow for
those systems whose components can be easily
separated from the purge gas.

NEW DIRECTIONS FOR GAS ADSORPTION

It is unlikely that gas adsorption will ever
rival the vapor-liquid separations in frequency
of use in the natural-gas, petroleum,
petrochemical and related industries.
Nevertheless, gas adsorption will continue to
make inroads as its technological limits are
more closely approached. Gas adsorption's
serious competition for the separations where it
is now used will come chiefly from
fixed-membrane processes. The extent of the
inroad cannot yet be discerned. Below we will
point out the likely areas of growth for gas

Displacement-purge cycles will not find many

new uses, primarily because of the inherent
complexity of these cycles.

523
Proceedings from the Sixth Annual Industrial Energy Technology Conference Volume II, Houston, TX, April 15-18, 1984

ESL-IE-84-04-88

[3] Sak aguch i, Y., Chemica 1 Economy and

Fixed-bed, temperature-swing processes

rarely turn out to be economical for bulk
separations. Moving-bed and fluidized-bed
processes based on thermal regeneration may
prove to be much more economical because of
lower heat requirements per unit of feed. The
key to the success of these processes lies in
the development of highly-attrition-resistant
adsorbent particles.

Engineering Review
(December, 1976).

~,

No. 12, 36

[4] Anon., Chemical Engineering, 39

(August 29, 1977).

[5] "PURASIV HR for Hydrocarbon Recovery",

Union Carbide Corporation, Danbury, CT.

[6J Knoblauch, K., Chemical Engineering, 87

(November 6, 1978).

Some other areas of new or expanded use for

gas adsorption include synthesis gas ratio
adjustment, carbon dioxide recovery from oil
and gas-field streams. ammonia process
vent-recovery, and purging of inerts from
chemical-process streams.

[7] "Pure Nitrogen Generator", Gas Services

International, Ltd., Enfield, Middlesex,

England.

[ 8J Miwa, K., and T. Inoue, Chemical Economy

and Engineering Review 12, No. 11, 40

(November, 1980).

I
[9J Sircar, S., and J. W. Zondlo, U. S. Patent
4.013,429, March 22, 1977.
I
[lOJ Heck, J. L., and T. Johansen, Hydrocarbon
Processing. 175 (January, 1978).

Gas Purification - It is not likely that many

process innovations will be needed for these
separations. Fixed-bed, temperature-swing
processes will continue to predominate, although
moving-bed and fluidized-bed processes such as
PURASIV HR should become more popular. Air
pollution concerns should bring about increased
applications for recovery of organics from
various process vent streams, storage-tank
vents. and air streams from solvent-pointing and
other operations involving vaporization of
organics. Major-use areas such as gas
dehydration, removal of sulfur compounds and
carbon dioxide and various specialty separations
will grow about in proportion to the growth of
those industries in which these separations are
found.

[11 ] Corr, F., Dropp, F., and E. Rudelstorferr,

Hydrocarbon Processing. 119 (March,

197~).

[12J Cassidy, R. 1., "POLYBED Pressure-Swing I

Adsorption Hydrogen Processing", in
Flank, W. H. (ed.), Adsorption and Ion
Exchange with Synthetic Zeolites, Ameridan
Chemical Society Symposium Series 135
(1980) .

References
[1] Berg, C., Petroleum Refiner 30, No.9, 241
(September,1951).

[13J Garg, D. R., and J. P. Ausikaitis, Chem4

Eng. Progress, 60 (Apri 1, 1983).

[2] Treybal, R. E., "Mass Transfer Operations",

McGraw-Hill (1955).

[14J Symoniak, Hydrocarbon Processing, 110 n-lay,

1980) .

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Proceedings from the Sixth Annual Industrial Energy Technology Conference Volume II, Houston, TX, April 15-18, 1984